Microplastic particles in arable soil are expected to impact the environment and potentially human health. The application of municipal biosolids (MBs) to agricultural land presents a further dilemma in that biosolids act as a fertilizer for crop growth, and a disposal pathway for wastewater treatment plants. They are also a direct path for emerging contaminants, such as microplastics to enter the terrestrial environment. Reliable methods are needed to identify and quantify microplastics, found in agricultural soils to determine how microplastics are being cycled in the terrestrial environment. In this study, we developed a method for extracting microplastics from soil, and characterized their composition and identity for particles sized 5 μm to 2 mm. Method development was initially completed using natural soils spiked with microplastics and MBs, followed by the analyses of soil sampled from an agricultural field where MBs were recently applied at a rate of 13 tons dw/ha. The procedures that used the spiked samples showed that microplastics can be reliably extracted from soil in a laboratory setting, and identified and semi-quantified by thermogravimetric analysis combined with Fourier-transform infrared spectroscopy (TGA-FTIR). However, when the same methods were applied to the soil samples collected from the agricultural field, reproducibility became a challenge, as the number and type of microplastics changed even within the same soils (i.e., collected the same day from the same exact location). The variation in reproducibility observed between laboratory and field samples underscores the significant heterogeneity present in the environment. This heterogeneity, in turn, affects the identification and quantity of microplastics detected, a phenomenon observed even when comparing different fields within a single treatment regimen.

We present a concurrent self-assembly strategy for patterning hierarchical polymeric surface features by depositing variable-composition blends of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) and polybutadiene-block-poly(ethylene oxide) (PB-b-PEO) block copolymers at the air-water interface. Hierarchical strand networks of hydrophobic PS/PB blocks anchored via PEO blocks to the water surface, with an internal phase-separation structure consisting of periodic domains of PS blocks surrounded and connected by a matrix of PB blocks, are generated by the interplay of interfacial amphiphilic block copolymer aggregation and polymer/polymer phase separation. In contrast to the cylinder-in-strand structures previously formed by our group in which interfacial microphase separation between PS and PB blocks was constrained by chemical connectivity between the blocks, in the current system phase separation between PS and PB is not constrained by chemical connectivity and yet is confined laterally within surface features at the air-water interface. Investigations of multi-component polymer systems with different connectivities constraining repulsive and attractive interactions provides routes to new hierarchical surface patterns for a variety of applications, including photolithography masks, display technology, surface-guided cell growth and tissue engineering.

Surface chemistry is an important factor for quality control during production of nanomaterials and for controlling their behavior in applications and when released into the environment. Here we report a comparison of four methods for quantifying amine functional groups on silica nanoparticles (NPs). Two colorimetric assays are examined, ninhydrin and 4-nitrobenzaldehyde, which are convenient for routine analysis and report on reagent accessible amines. Results from the study of a range of commercial NPs with different sizes and surface loadings show that the assays account for 50–100% of the total amine content, as determined by dissolution of NPs under basic conditions and quantification by solution-state H NMR. To validate the surface quantification by the colorimetric assays, the NPs are modified with a trifluoromethylated benzaldehyde probe to enhance sensitivity for quantitative F solid state NMR and X-ray photoelectron spectroscopy (XPS). Good agreement between the assays and the determination from solid-state NMR is reinforced by elemental ratios from XPS, which indicate that in most cases the difference between total and accessible amine content reflects amines that are outside the depth probed by XPS. Overall the combined results serve to validate the relatively simple colorimetric assays and indicate that the reactions are efficient at quantifying surface amines, by contrast to some other covalent modifications that have been employed for functional group quantification.

A mixed micelle approach is used to produce amphiphilic brush nanoparticles (ABNPs) with cadmium sulfide quantum dot (QD) cores and surface layers of densely grafted (σ = ~1 chain/nm2) and asymmetric (fPS = 0.9) mixed polymer brushes that contain hydrophobic polystyrene (PS) and hydrophilic poly(methyl methacrylate) (PMAA) chains (PS/PMAA-CdS). In aqueous media, the mixed brushes undergo conformational rearrangements that depend strongly on prior salt addition, giving rise to one of two pathways to fluorescent and morphologically disparate QD-polymer colloids. (A) In the absence of salt, centrosymmetric condensation of PS chains forms individual core-shell QD-polymer colloids. (B) In the presence of salt, non-centrosymmetric condensation of PS chains forms Janus particles, which trigger anisotropic interactions and amphiphilic self-assembly into the QD-polymer vesicles. To our knowledge, this is the first example of an ABNP building block that can form either discrete core-shell colloids or self-assembled superstructures in water depending on simple changes to the chemical conditions (i.e., salt addition). Such dramatic and finely tuned morphological variation could inform numerous applications in sensing, biolabeling, photonics, and nanomedicine.

The application of molecular self-assembly principles to nanoscopic building blocks can inform new pathways to hierarchical nanomaterials. For instance, amphiphilic brush nanoparticles (ABNPs) are inorganic nanoparticles functionalized with mixed polymer brushes of hydrophobic and hydrophilic chains that possess several structural and chemical features similar to those of amphiphilic block copolymers (ABCs), including spatial segregation of covalently connected hydrophilic and hydrophobic regions, anisotropic interactions, and conformational flexibility. However, the phase behavior of ABNPs with respect to hydrophobic fraction, concentration, and salt content has not been established to date, precluding direct comparison with ABC self-assembly. In this study, we produce and characterize a series of ABNPs with similar cadmium sulfide core sizes and brush densities but with different polystyrene/poly(methacrylic acid) brush compositions using a diblock copolymer mixed micelle approach. Self-assembly of the resulting ABNPs in THF/water mixtures yields hybrid spheres, cylinders, and vesicles with morphological transitions following trends with respect to hydrophobic fraction, initial concentration, and salt content similar to those previously established for ABCs. The resulting ABNP phase behavior demonstrates that microphase separation principles established in the 1990s for the solution self-assembly of macromolecular ABCs can provide vital experimental guidelines for the controlled self-organization of nanoscopic amphiphiles.

Single-layered graphene oxide (GO) has exhibited great promise in the areas of sensing, membrane filtration, supercapacitors, bioimaging, and therapeutic carriers because of its biocompatibility, large surface area, and electrochemical, photoluminescent, and optical properties. To elucidate how the physical dimensions of GO affect its intrinsic properties, we employed sonication to produce more than 130 different sizes of GO in aqueous dispersion and implemented new approaches to characterize various GO properties as a function of the average flake size. New protocols were developed to determine and compare the flake size of GO dispersions sonicated with energies up to 20 MJ/g by using dynamic light scattering and atomic force microscopy (AFM). The relationship between the average flake size and sonication energy per unit mass of GO was observed to follow a power law. AFM height measurements showed that the sonication of GO yielded monolayered flakes. Photoluminescence of GO was characterized as a function of the sonication energy (or the average flake size which is the monotonic function of the sonication energy), excitation wavelength, and pH of the dispersion. The strong dependence of the photoluminescence intensity on pH control and the variation of the photoluminescence intensity with different flake sizes were observed. An intense photoluminescence signal, likely related to the separation of the oxidative debris from the GO framework, was found at the highest sonication energies (E ≳ 15 MJ/g) or under extremely alkaline conditions (pH ≳ 11). The cytotoxicity of GO was studied with various flake sizes. Size- and concentration-dependent cytotoxicity was observed for cell lines NIH 3T3 and A549. The NIH 3T3 cell line also demonstrated time-dependent cytotoxicity.

Despite significant advances in single-walled carbon nanotube (SWNT) synthesis and purification strategies, the separation of metallic and semiconducting SWNTs on a large scale remains a barrier to the realization of many commercial applications. Selective extraction of specific SWNT types by wrapping and dispersion with conjugated polymers has been found effective for semiconducting SWNTs, but structural parameters that dictate selectivity are poorly understood. Here, we report nanotube dispersions with two structurally similar conjugated copolymers, both being poly(fluorene-co-phenylene) derivatives, having comparable degrees of polymerization but differing in the extent of electron donation from functional groups on the phenylene comonomers. It is found that copolymers decorated with electron donating methoxy functionalities lead to predominant dispersion of semiconducting SWNTs, while copolymers decorated with electron withdrawing nitro functionalities bias the dispersion toward metallic SWNTs. Differentiation of semiconducting and metallic SWNT populations was carried out by a combination of UV-vis-NIR absorption spectroscopy, Raman spectroscopy using multiple excitation wavelengths, and fluorescence spectroscopy. These results provide new insight into polymer design features that dictate preferential dispersion of specific SWNT types.